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Acid- And base-switched palladium-catalyzed γ-C(sp3)-H alkylation and alkenylation of neopentylamine
The functionalization of remote unactivated C(sp3)-H and the reaction selectivity are among the core pursuits for transition-metal catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)-H-selective alkylation and alkenylation with removable 7-azaindole as a directing group. Acid and base were found to be the decisive regulators for the selective alkylation and alkenylation, respectively, on the same single substrate under otherwise the same reaction conditions. Various acrylates were compatible for the formation of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. The alkenylation protocol could be further extended to acrylates with natural product units and α,β-unsaturated ketones. The preliminary synthetic manipulation of the alkylation and alkenylation products demonstrates the potential of this strategy for structurally diverse aliphatic chain extension and functionalization. Mechanistic experimental studies showed that the acidic and basic catalytic transformations shared the same six-membered dimer palladacycle.
Zhang, Jinquan,Zhang, Shuaizhong,Zou, Hongbin
supporting information
p. 3466 - 3471
(2021/05/31)

Palladium-catalyzed remote C-H functionalization of 2-aminopyrimidines
A straightforward strategy was developed for the arylation and olefination at the C5-position of the N-(alkyl)pyrimidin-2-amine core with readily available aryl halides and alkenes, respectively. This approach was highly regioselective, and the transformation was achieved based on two different (Pd(ii)/Pd(iv)) and (Pd(0)/Pd(ii)) catalytic cycles.
Das, Animesh,Jana, Akash,Maji, Biplab
supporting information
p. 4284 - 4287
(2020/04/27)

Synthesis of Some Aromatic and Aliphatic Esters Using WO3/ZrO2 Solid Acid Catalyst under Solvent Free Conditions
A simple method is delineated for the synthesis of substituted ester products in superior yields by esterification reaction under solvent unbound condition using tungsten upgraded ZrO2 solid acid catalyst at 353 K. The WO3/ZrO2 catalyst has been prepared by using impregnation method followed by calcination at 923 K over a period of 6 h in air atmosphere. SEM, XRD, FTIR, and BET surface area techniques were used to categorize this catalyst. Zirconia has both acidic and basic possessions which can be changed by incorporating suitable promoter atom like tungsten which in turn increases the surface area thereby enhancing the surface acidity. Impregnation of W6+ ions exhibits a strong influence on phase modification of zirconia from thermodynamically solid monoclinic to metastable tetragonal phase. Amalgamation of promoter W6+ will stabilize tetragonal phase which is active in catalyzing reactions. In esterification reaction WO3/ZrO2 catalyst was found to be stable, efficient and environmental friendly, effortlessly recovered by filtration, excellent yield of product and can be reusable efficiently.
Guguloth, Vijaya Charan,Battu, Satyanarayana
p. 2153 - 2157
(2020/09/16)

Second-Generation meta-Phenolsulfonic Acid-Formaldehyde Resin as a Catalyst for Continuous-Flow Esterification
A second-generation m-phenolsulfonic acid-formaldehyde resin (PAFR II) catalyst was prepared by condensation polymerization of sodium m-phenolsulfonate and paraformaldehyde in an aqueous H2SO4 solution. This reusable, robust acid resin catalyst was improved in both catalytic activity and stability, maintaining the characteristics of the previous generation catalyst (p-phenolsulfonic acid-formaldehyde resin). PAFR II was applied in the batchwise and continuous-flow direct esterification without water removal and provided higher product yields in continuous-flow esterification than any other commercial ion-exchanged acid catalyst tested.
Hu, Hao,Ota, Hajime,Baek, Heeyoel,Shinohara, Kenta,Mase, Toshiaki,Uozumi, Yasuhiro,Yamada, Yoichi M. A.
supporting information
p. 160 - 163
(2020/01/02)

Safe production process of butyl acrylate
The invention relates to a safe production process of butyl acrylate, belonging to the technical field of organic synthesis. According to the invention, acrylic acid is used as an initial raw material; acrylate is prepared firstly; and then the acrylate reacts with bromobutane to synthesize the butyl acrylate. The safe production process has the following beneficial effects: (1) the use of acidicsubstances is avoided, and the corrosion of the acidic substances to pipelines is prevented; (2) reaction temperature is reduced; and (3) rectification separation effect is better, and the separated bromobutane can be repeatedly utilized.
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Paragraph 0027-0046

(2020/07/15)

Palladium-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted: O-carboranes containing α,β-unsaturated carbonyls
With the help of a carboxylic acid directing group, Pd-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted o-carboranes containing α,β-unsaturated carbonyls has been reported. The-COOH, removed during the course of the reaction, is responsible for controlling the regioselectivity. The desired products could be obtained in moderate to good yields.
Li, Jiaoyi,Lu, Jian,Tian, Song,Wang, Qian,Zhang, Chuyi,Zhang, Jianwei,Zhou, Ling
p. 4723 - 4727
(2020/07/13)

Acrylate Esters by Ethenolysis of Maleate Esters with Ru Metathesis Catalysts: an HTE and a Technoeconomic Study
A high throughput experimentation (HTE) study identified active Ru metathesis catalysts and reaction conditions for the ethenolysis of maleate esters to the respective acrylate esters. Catalysts were tested at various loadings (75–10’000 ppm) and temperatures (30–60 °C) with maleate esters dissolved in toluene (up to ca. 44 wt-%) or neat and at variable partial pressures of ethylene (0.2–10 bar). Ruthenium catalysts containing a PCy3 ligand, such as 1st or 2nd generation Grubbs catalysts, as well as the state-of-the-art catalysts containing cyclic alkyl amino carbene (CAAC) ligands, are generally inferior to Hoveyda–Grubbs 2nd generation catalyst in ethenolysis of maleates. Productive turnover numbers could exceed 1900 if the ethenolysis reaction is performed at low ethylene pressure (0.2–3 bar) and reach 5200 when a polymeric phenol additive was used. Such catalytic performance falls well within the window practiced in industry. Moreover, a crude technoeconomic analysis finds similar production cost for the ethenolysis route and conventional technology, that is, propene oxidation followed by esterification, justifying research to further improve the ethenolysis route.
Copéret, Christophe,De Jesus Silva, Jordan,Engl, Pascal S.,Fedorov, Alexey,Lange, Jean-Paul,Togni, Antonio,Tsygankov, Alexey
(2020/04/29)

PRODUCTION METHOD OF (METH)ACRYLIC ACID ESTER
PROBLEM TO BE SOLVED: To provide a method of producing (meth)acrylic acid ester stably and efficiently over a long term by separating (meth)acrylic acid ester and a heavy component from an esterification reaction liquid containing (meth)acrylic acid ester obtained by reacting (meth)acrylic acid and alcohol under the presence of an acid catalyst, by preventing formation of an origin of contamination at an operation start time of a heavy decomposer that recovers valuable matters by decomposing and causing an esterification reaction of the heavy component, and by effectively reflecting condition adjustment for contamination/closure during an operation thereafter. SOLUTION: When recovering valuable matters containing (meth)acrylic acid ester and alcohol by decomposing, and making esterification reaction by introducing a mixed liquid of the heavy component and an acid catalyst-containing liquid in the heavy decomposer, introduction of the heavy component into the heavy decomposer is started, and after an internal temperature has reached 80°C or higher by heating, the acid catalyst solution is supplied to the heavy decomposer. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0045-0049

(2019/12/04)

Ruthenium(II) oxidase catalysis for C-H alkenylations in biomass-derived γ-valerolactone
Ruthenium(ii) biscarboxylate oxidase catalysis is a powerful tool for the assembly of functionalized arenes with oxygen as a green oxidant, but this strategy was thus far limited to its use in traditional organic solvents. Herein, we report on a green procedure for the ruthenium(ii) biscarboxylate-catalysed C-H functionalisation in biomass-derived γ-valerolactone as the reaction medium. The oxidase catalysis was characterized by ample substrate scope and proceeded efficiently with oxygen as the sole oxidant. The overall green nature of this C-H-activation methodology is reflected by H2O being the only by-product.
Bechtoldt, Alexander,Baumert, Marcel E.,Vaccaro, Luigi,Ackermann, Lutz
supporting information
p. 398 - 402
(2018/02/07)

Method for synthesizing low-carbon alcohol acrylate from acetylene through carbonylation
The invention relates to a method for synthesizing low-carbon alcohol acrylate from acetylene through carbonylation. The method comprises steps as follows: acetylene, low-carbon alcohol and carbon monoxide are taken as raw materials and added to an organic solvent containing a nickel-based catalyst, low-carbon alcohol acrylate is directly synthesized from the mixture through carbonylation, whereinthe nickel-based catalyst comprises a main catalyst, an additive and a catalyst promoter, the main catalyst contains a nickel-containing compound and a multidentate ligand, the additive is triphenylphosphine, the chemical formula of the catalyst promoter is AlR(3-x)Clx, R is C2-C8 alkyl, and x is larger than or equal to 0 and smaller than or equal to 1. Compared with the prior art, the catalyticsystem is non-toxic and non-corrosion to equipment; yield of products at lower temperature and pressure is high, particularly, the catalyst system is low in cost and simple to prepare, cost of raw materials of production and operation cost can be greatly reduced, and the method has broad industrial application prospect.
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Paragraph 0041-0044

(2018/05/30)

(Meth) acrylic acid ester
PROBLEM TO BE SOLVED: To provide a method for producing a (meth)acrylic acid ester stably and efficiently over a long period of time by preventing distillation operation trouble in a low boiling point fraction-separating tower in which an esterification solution containing a (meth)acrylic acid ester obtained by reacting (meth)acrylic acid with alcohol in the presence of an acid catalyst is neutralized and washed and then an oil layer obtained by separating the resulting solution into an oil layer and a water layer is sequentially fed into a low boiling point fraction-separating tower and a purifying tower.SOLUTION: When an esterification solution is neutralized and washed in a (meth)acrylic acid separation tower and neutralizing and washing treatment liquid is allowed to stand in a still standing tank to separate into an oil layer and a water layer, an oil and water mixed liquid at an interface region between the oil layer and the water layer in the (meth)acrylic acid separation tower and/or the still standing tank is taken out to feed into a storage tank and left at rest for a predetermined time. Then, the oil phase is returned to a reactor and/or the (meth)acrylic acid separation tower.
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Sheet 0044

(2017/12/01)

Method for carbonylation-synthesizing acrylic ester by acetylene
The invention discloses a method for carbonylation-synthesizing acrylic ester by acetylene, and relates to the technical field of the organic synthesis. The method comprises the following steps: using the acetylene, carbon monoxide and lower alcohol as reaction raw materials, under the action of a catalyst, executing the acetylene carbonylation reaction in a solvent and directly generating the acrylic ester, wherein the catalyst is a nickel non-halogen compound and a salt ligand of Beta-diketone and corresponding compounds. An original method for synthesizing the acrylic ester has the problems, such as long reaction time, carbon deposition in the reaction process and serious corrosion of devices. The method has the advantages of easy acquisition of used catalyst components, rapid catalytic reaction speed, short used time, no carbon deposition in the reaction process, and no device corrosion by a catalyst system.
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Page/Page column 5-6

(2018/03/01)

Method for synthesizing acrylic acid low-carbon alcohol ester through carbonylation of acetylene
The invention relates to a method for synthesizing acrylic acid low-carbon alcohol ester through carbonylation of acetylene. A nickel-containing compound and a bidentate ligand containing nitrogen and a VIA-th group element serve as catalysts, and acetylene, carbon monoxide and low-carbon alcohol are subjected to carbonylation reaction in a solvent to synthesize the acrylic ester at one step. The method has the characteristics of low catalyst cost, high reaction speed, no carbon deposition in the reaction process and the like.
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Paragraph 0037-0038

(2017/08/29)

Enhanced Acrylate Production from 2-Acetoxypropanoic Acid Esters
Reaction conditions and reactor geometry for producing acrylates in high yield from lactic acid-derived 2-acetoxypropanoic acid (APA) esters are presented. An acrylate ester yield of 75% is achieved from methyl and benzyl APA esters at 550 °C in a fixed bed reactor filled with nonporous silica particles, carbon dioxide as a diluent gas, and acetic acid as a co-feed with the APA ester. The yield from methyl and benzyl APA esters is remarkably higher than from ethyl or butyl esters of APA, which have hydrogen atoms on the β-carbon of the ester functional group and thus can undergo alkene elimination, leading to reduced acrylate yield. Under optimum conditions, APA conversion to acrylates is stable over 30 h of continuous operation with little carbon deposition on the contact material.
Nezam, Iman,Peereboom, Lars,Miller, Dennis J.
p. 715 - 719
(2017/05/29)

(Meth) acrylic acid ester
PROBLEM TO BE SOLVED: To provide a method for producing a (meth)acrylic acid ester stably and efficiently over a long period of time by preventing distillation operation trouble in a low boiling point fraction-separating tower in which an esterification solution containing a (meth)acrylic acid ester obtained by reacting (meth)acrylic acid with alcohol in the presence of an acid catalyst is neutralized and washed and then an oil layer obtained by separating the resulting solution into an oil layer and a water layer is sequentially fed into a low boiling point fraction-separating tower and a purifying tower.SOLUTION: A water droplet capturing member is provided between an oil and water interface in the (meth)acrylic acid separation tower used for neutralization and washing and/or the still standing tank used for oil and water separation and a liquid extraction opening.
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Paragraph 0050-0052

(2018/03/23)

System and method for preparing acrylic acid lower alcohol ester from acetylene
The invention discloses a system and method for preparing acrylic acid lower alcohol ester from acetylene. The system comprises an acetylene dissolution tank, a reactor, a first gas-liquid separator, a second gas-liquid separator, a carbon monoxide extraction device and a compressor. The acetylene dissolution tank is provided with an acetylene inlet, a non-polar organic solvent inlet and a liquid outlet. The reactor comprises an acetylene solvent inlet, a carbon monoxide gas inlet and a gas outlet. The first gas-liquid separator comprises a gas inlet, a gas outlet and an acrylic acid lower alcohol ester outlet. The second gas-liquid separator comprises a gas inlet and a gas outlet. The product, by-products and a solvent can be separated by means of different distillation temperatures; besides, carbon monoxide and the organic solvent are recycled, so that raw materials are saved, and cost is lowered.
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Paragraph 0058; 0059

(2017/06/13)

1,4-Diazabicyclo[2.2.2]octane-Promoted Aminotrifluoromethylthiolation of α,β-Unsaturated Carbonyl Compounds: N-Trifluoromethylthio-4-nitrophthalimide Acts as Both the Nitrogen and SCF3 Sources
A novel difunctionalization reaction is described. It uses N-trifluoromethylthio-4-nitrophthalimide as the reagent, which serves as both the nitrogen and SCF3 sources. In the presence of DABCO (1,4-diazabicyclo[2.2.2]octane), the nitrogen and SCF3 groups can be incorporated into α,β-unsaturated carbonyl compounds easily and give versatile β-amino ketones and esters in good yields. This difunctionalization reaction features mild reaction conditions, high atom-economy, and efficient access to α-SCF3 amino acids.
Xiao, Qing,He, Qijie,Li, Juncheng,Wang, Jun
supporting information
p. 6090 - 6093
(2016/01/09)

METHOD FOR PRODUCING BUTYL ACRYLATE
PROBLEM TO BE SOLVED: To provide an efficient method for removing by-produced dibutyl ether in order to, in a production process of butyl acrylate, mitigate restrictions on an esterification reaction and a heat decomposition reaction, which are for suppressing by-production of dibutyl ether. SOLUTION: Provided is a method for continuously producing butyl acrylate, comprising: an esterification reaction step of obtaining a reaction mixture by an esterification reaction of acrylic acid and butanol in a reactor in the presence of an acid catalyst, and continuously separating the reaction mixture under reduced pressure into crude butyl acrylate and a volatile component; a distillation step of distilling the volatile component in a reactive distillation column, returning a discharge component to the reactor, separating a distillate component into an organic layer and an aqueous layer, and circulating the organic layer into the reactive distillation column; and a purification step of obtaining butyl acrylate by distillation purification of the crude butyl acrylate. In the distillation step, a part of the organic layer is distilled in a separation distillation column while forming two liquid layers of an aqueous layer and an organic layer by supplying water, and at least a part of a distillate component is removed out of the system. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0047

(2016/12/22)

METHOD FOR PRODUCING BUTYL ACRYLATE
PROBLEM TO BE SOLVED: To provide a continuous production method of butyl acrylate which suppresses an amount of butyl 3-butoxypropionate produced and improves the reaction conversion rate of acrylic acid, with an aim to carry out a more efficient esterification reaction in series multistage reactive distillation using acrylic acid and butanol. SOLUTION: The method for producing butyl acrylate comprises: a reaction step of reacting acrylic acid and butanol using multistage reactors in series to obtain a reaction mixture containing butyl acrylate; and a distillation step of separating the butyl acrylate from the reaction mixture containing butyl acrylate, produced in the reaction step, by distillation using a distillation column. In the reaction step, a heat quantity of a heat source, supplied to at least the downstream-most reactor of the multistage reactors in series, is maintained substantially constant. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0030

(2016/12/26)

METHOD FOR PRODUCING BUTYL ACRYLATE
PROBLEM TO BE SOLVED: To provide a method for producing butyl acrylate which, when removing acrylic acid from butyl acrylate containing a small amount of acrylic acid by neutralization and washing with water, enables reduction of an amount of water used for the operation without increasing concentrations of acrylic acid and a neutralized salt in butyl acrylate after washing. SOLUTION: Provided is a method for producing butyl acrylate comprising: a formation step of forming a reaction mixture containing crude butyl acrylate by reacting acrylic acid and butanol; a neutralization step of neutralizing the reaction mixture; and a washing step of washing the reaction mixture using a washing liquid, the reaction mixture having been neutralized in the neutralization step, where, in the washing step, the washing liquid is a 0.7 to 5.5 wt% aqueous butanol solution. Specifically provided is the method for producing butyl acrylate, in which the washing liquid is a 1.7 to 5.5 wt% aqueous butanol solution, further containing 0.2 wt% or less acrylic acid and 0.2 wt% or less sodium hydroxide. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0041

(2018/02/03)

Oxo-rhenium-catalyzed deoxydehydration of polyols with hydroaromatic reductants
Several dihydroaromatic compounds are shown to be effective reducing agents in the oxo-metal-catalyzed deoxydehydration of diols and polyols to produce olefins and the corresponding arenes. NH4ReO4 and MeReO3 are active catalysts for the reactions. The most effective of the hydroaromatic reductants is indoline, which is oxidized to indole. Yields for a variety of diols and polyols range from 35% to 99%. Two hydrogen donors, 1,3-cyclohexadiene and dihydroanthracene, engage in tandem DODH/cycloaddition reactions. Competition experiments show that indoline is more reactive than representative alcohols in H-transfer. Indoline is shown to reduce MeReO3 to MeReO2 via an isolable adduct, MeReO3(indoline) (4), which has been structurally characterized and is suggested to be an intermediate in the catalytic DODH process.
Boucher-Jacobs, Camille,Nicholas, Kenneth M.
supporting information
p. 1985 - 1990
(2015/06/08)

Acrylates via Metathesis of Crotonates
Crotonic acid has the potential to be produced from renewable resources at low cost but currently has a limited market. We are investigating catalytic routes to exploit the functionalities of crotonic acid to produce a range of established industrial chemicals. Here we report our work on converting crotonates to acrylates, where a cost-competitive bio-based alternative can provide a market advantage. Our optimized reaction conditions for the cross-metathesis between crotonates and ethylene resulted in an increase in catalyst turnover numbers by 2 orders of magnitude compared with literature values. Control experiments showed the cross-metathesis with ethylene to be an equilibrium reaction. The turnover-number-limiting factor was found to be the stability of the metathesis catalyst.
Schweitzer, Dirk,Snell, Kristi D.
supporting information
p. 715 - 720
(2015/07/27)

METHOD FOR PRODUCING ACROLEIN, ACRYLIC ACID, AND DERIVATIVE THEREOF
A process for producing acrolein, comprising: a glycerin dehydration step of conducting dehydration reaction of glycerin to obtain an acrolein-containing gas; a partial-condensation step of cooling the acrolein-containing gas to condense a part of acrolein, water and a high-boiling substance contained in the acrolein-containing gas, thereby obtaining a purified gas and a condensate; and a separation step of separating the purified gas from the condensate; wherein a polymerization inhibitor is added to the acrolein-containing gas or the condensate in the partial-condensation step.
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Paragraph 0125

(2014/08/19)

Room temperature hydrophosphination using a simple iron salen pre-catalyst
Phosphines are fundamentally important to the fine chemicals, pharmaceutical and agrochemical industries. Reported is the first example of alkene hydrophosphination using a designed iron pre-catalyst which yields the anti-Markovnikov products in high yield at room temperature. The phosphine products are excellent pro-ligands for Fe-catalyzed Negishi cross-coupling. This journal is
Gallagher,Webster
supporting information
p. 12109 - 12111
(2015/01/08)

PROCESS FOR MAKING CHEMICAL DERIVATIVES
Process and methods for making glycolic acid chemical intermediates and derivatives from biomass are described herein.
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Paragraph 0160; 0162

(2014/02/16)

SYNTHESIS OF OLEFINS
Described herein are methods for producing 1,3-butadiene and one or more of acrylic acid and esters of acrylic acid from muconic acid or a derivative thereof.
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Paragraph 00168

(2013/06/27)

METHOD OF PREPARING ALKYL (METH)ACRYLATE
The present invention relates to a method of preparing an alkyl (meth)acrylate, and more specifically to a method of preparing an alkyl (meth)acrylate which comprises the steps of: carrying out an esterification reaction with reactants comprising an alkanol and (meth)acrylic acid in the presence of an organic acid catalyst with a conversion rate of about 70% or more; supplying reaction products of the esterification reaction to a distillation tower equipped with a reboiler at the lower end to purify them; recovering a upper discharge comprising an alkyl (meth)acrylate and water at the upper part of the distillation tower and recovering a lower discharge comprising high boiling materials and water at the lower part of the distillation tower; separating the lower discharge of the distillation tower into a water layer and an organic layer; and recirculating the water layer separated from the lower discharge so as to be used in the esterification reaction, wherein each of the steps occurs continuously and the lower discharge of the distillation tower includes water in an amount of about 2-25% by weight with respect to the total weight of the lower discharge.
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Page/Page column 26-28

(2012/03/26)

ACRYLATE PRODUCTION PROCESS
A process comprising for preparing C1 to C4 alkyl (meth)acrylates, such as butyl acrylate, wherein vaporized reactor contents are fed directly to a column, the aqueous reflux ratio to the column is from 4 to 12, and the level of acrylic acid in the primarily organic phase separated from the overhead condensate of the column is less than 2000 ppm.
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Page/Page column 8-10

(2012/06/15)

COMPOSITION INCLUDING DIALKYL TIN OXIDE AND USE THEREOF AS A TRANSESTERIFICATION CATALYST FOR THE SYNTHESIS OF (METH) ACRYLIC ESTERS
The present invention relates to a composition including a dialkyl tin oxide, such as DBTO, which can be used as a transesterification catalyst for the synthesis of (meth)acrylic esters. The invention also relates to a method for the synthesis of (meth)acrylic esters by transesterification in the presence of said composition.
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Page/Page column 4

(2012/05/21)

Simultaneous production of biobased styrene and acrylates using ethenolysis
Phenylalanine (1), which could be potentially obtained from biofuel waste streams, is a precursor of cinnamic acid (2) that can be converted into two bulk chemicals, styrene (3) and acrylic acid (4), via an atom efficient pathway. With 5 mol% of Hoveyda-Grubbs 2nd generation catalyst, 1 bar of ethylene, and using dichloromethane as solvent, cinnamic acid (2) can be converted to acrylic acid and styrene at 40 °C in 24 h with 13% conversion and 100% selectivity. Similar results are obtained using cinnamic acid esters (methyl, ethyl and n-butyl) as substrates and optimisation leads to higher conversions (up to 38%). For the first time, cross-metathesis of these types of electron deficient substrates was achieved.
Spekreijse, Jurjen,Le Notre, Jerome,Scott, Elinor L.,Sanders, Johan P. M.,Van Haveren, Jacco
supporting information
p. 2747 - 2751,5
(2020/09/14)

Catalytic decarbonylation of biomass-derived carboxylic acids as efficient route to commodity monomers
The palladium-catalyzed decarbonylation of bio-derived carboxylic acids to alkyl acrylates, styrene, and acrylonitrile is reported. The olefins were isolated by continuous distillation in yields up to 87% by heating a neat, equimolar mixture of pivalic anhydride with the appropriate carboxylic acid to 190 °C in the presence of a Pd-phosphine catalyst.
Miranda, Maria O.,Pietrangelo, Agostino,Hillmyer, Marc A.,Tolman, William B.
experimental part
p. 490 - 494
(2012/04/10)

Preparation Method for (Meth)acrylate
The present invention provides a method for preparing (meth)acrylate by esterification reaction of reactants containing (meth)acrylic acid and alcohol in the presence of a catalyst, the preparation method for (meth)acrylate is characterized in that a hydrazine compound or derivative thereof is put into an esterification reactor; and (meth)acrylate prepared by the same. The present invention effectively prevents impurities generated by aldehyde that is contained in the raw material (meth)acrylic acid from remaining in a production apparatus and the catalyst, so that the process for producing (meth)acrylate proceeds smoothly.
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Page/Page column 3

(2011/04/18)

Esterification of carboxylate-based ionic liquids with alkyl halides
A facile reaction of 1-ethyl-3-methylimidazolium acetate ([EMIm]Ac) with dichloromethane at room temperature was observed with esters among the products. This esterification can be exploited for mild solvent-free esterification with a range of other carboxylate-based ionic liquids and alkyl halides. The Royal Society of Chemistry.
Zhao, Bin,Greiner, Lasse,Leitner, Walter
scheme or table
p. 2973 - 2975
(2011/04/24)

Cycloaddition of zirconacyclopentadiene with 2-bromoacrylate, 2-bromoacrylaldehyde, and 3-bromofuran-2,5-dione in the presence of cucl: A new pathway for the formation of benzene derivatives and isobenzofuran-1,3-dione
Reaction of zirconacyclopentadienes with 2-bromoalkenes in the presence of CuCl afforded multisubstituted benzene derivatives. The reactions of 2-bromoacrylate and 2-bromo-3-phenylacrylaldehyde afforded penta-and hexasubstituted benzenes in good yields. The reaction of 3-bromofuran-2,5-dione with zirconacyclopentadienes gave isobenzofuran-1,3-diones in good yields. Copyright Taylor & Francis Group, LLC.
Chen, Chao,Yan, Xiaoyu,Xi, Chanjuan
experimental part
p. 570 - 579
(2010/04/06)

Kinetics of the synthesis of propyl and butyl acrylates in the presence of some heteropolyacids as catalysts
Esterification reactions of acrylic acid with n-propanol and n-butanol were carried out in the liquid phase in the presence of H3PW 12O40 or H3PMo12O40 as a catalyst, at various temperatures, molar ratios of the reactants, and concentrations of the catalyst. The kinetic equations had a nonelementary form.
Skrzypek, Ierzy,Witczak, Teresa,Grzesik, MirosLaw,Witczak, Mariusz
scheme or table
p. 12 - 17
(2009/04/07)

Silica-Supported zirconium complexes and their polyoligosilsesquioxane analogues in the transesterification of acrylates: Part 2. activity, recycling and regeneration
The catalytic activity of both supported and soluble molecular zirconium complexes was studied in the transesterification reaction of ethyl acrylate by butanol. Two series of catalysts were employed: three well defined silica-supported acetylacetonate and n-butoxy zirconium(IV) complexes linked to the surface by one or three siloxane bonds, (=SiO)Zr(acac)3 (1) (=3iO)3Zr(acac) (2) and (=SiO)3Zr(0-n-Bu) (3), and their soluble polyoligosilsesquioxy analogues (c-C5H9) 7Si8O12(CH3)2Zr(acac) 3 (I'), (c-C5Hc,)7Si7O 12Zr(acac) (Z'), and (cC5Hg)7Si 7O12Zr(O-W-Bu) (3'). The reactivity of these complexes were compared to relevant molecular catalysts [zirconium tetraacetylacetonate, Zr(acac)4 and zirconium tetra-n-butoxide, Zr(O-n-Bu)4]. Strong activity relationships between the silica-supported complexes and their polyoligosilsesquioxane analogues were established. Acetylacetonate complexes were found to be far superior to alkoxide complexes. The monopodal complexes 1 and V were found to be the most active in their respective series. Studies on the recycling of the heterogeneous catalysts showed sig-nificant degradation of activity for the acetylacetonate complexes (1 and 2) but not for the less active tripodal alkoxide catalyst, 3. Two factors are thought to contribute to the deactivation of catalyst: the lixivation of zirconium by cleavage of surface siloxide bonds and exchange reactions between acetylacetonate ligands and alcohols in the substrate/product solution. It was shown that the addition of acetylacetone to the low activity catalyst Zr(O-M-Bu)4produced a system that was as active as Zr(acac)4. The applicability of ligand addition to heterogeneous systems was then studied. The addition of acetylacetone to the low activity solid catalyst 3 produced a highly active catalyst and the addition of a stoichiometric quantity of acetylacetone at each successive batch catalytic run greatly reduced catalyst deactivation for the highly active catalyst 1.
Salinier, Valerie,Niccolai, Geraldp,Dufaud, Veronique,Basset, Jean-Marie
experimental part
p. 2168 - 2177
(2009/12/26)

PROCESS FOR RECOVERING SULFONIC ACID CATALYST AND NOBLE PRODUCTS FROM ACRYLATE HEAVY ENDS
Sulfonic acid catalyst, e.g., methanesuifonic acid (MSA), and noble products, e.g., acrylic acid, butanol and butyl acrylatε, are recovered from acrylatc reactor blowdown. The blowndown comprises, among oilier things, the Michael ad ducts of the sulfonic acid and acrylate esters. The blowdown is mixed with water, subjected to conditions sufficient to crack or hydrolyze the Michael addυcts into their constitueut parts. These cracking conditions are also sufficient to allow the recovery of the sulfonic acid and constituent parts, as well as other light components of the heavy ends, e.g., unreacted acrylic acid and butanol,
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Page/Page column 14-17

(2009/08/16)

Method For Making Alkyl (Meth) Acrylates by Direct Esterification
The invention concerns a improved method for making linear, branched or cyclic C1-C15 alkyl(meth)acrylates, by direct esterification of (meth)acrylic acid with a corresponding alcohol, said reaction being catalyzed by sulfuric acid. The method includes a step of hydrolyzing the neutralizing aqueous flow followed by extraction of the residual (meth)acrylic acid with solvent consisting entirely or partly of the alcohol used in the reaction. The invention enables organic pollution (COD) released in the final aqueous effluents of the process to be reduced, as well as productivity to be increased.
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Page/Page column 4

(2008/12/07)

PROCESS FOR THE MANUFACTURE OF C1 -C4 ALKYL (METH)ACRYLATES
The invention relates to an improved process for the manufacture of C1-C4 alkyl (meth)acrylates by a direct esterification of (meth)acrylic acid by the corresponding alcohol in the presence of sulphuric acid, phenothiazine being used as polymerization inhibitor. The said process comprises a stage of recovering in value the heavy byproducts generated during this manufacture which consists of a distillation at a relatively low temperature and under an inert atmosphere, followed by a catalytic cracking under an inert atmosphere.
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Page/Page column 4

(2008/06/13)

Process for producing easily polymerizable substance
It is an object of the present invention to provide a process for producing easily polymerizable substance, which can realize stable operation of a purification system, and can stably maintain a production amount by avoiding production stoppage, upon production of an easily polymerizable substance in plural reactors. The present invention is directed to a process for producing easily polymerizable substance, which comprises mixing easily polymerizable substances obtained in plural reactors in advance, and supplying the mixture to a purification apparatus.
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Page/Page column 21

(2008/06/13)

N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds, their corresponding N-oxides and controlled radical polymerization therewith
The present invention relates to selected 1-alkoxy-2,2,6,6 tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine derivatives which are substituted in the 4 position by two oxygen atoms forming an open chain or cyclic ketal structure, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) said piperidine derivatives. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of 1-alkoxy-2,2,6,6 tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine derivatives which are substituted in the 4 position by two oxygen atoms forming an open chain or cyclic ketal structure for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator, as well as a process for polymerization are also subjects of the present invention.
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(2008/06/13)

Asymmetric Diels-Alder reaction between acrylates and cyclopentadiene in the presence of chiral catalysts
Asymmetric Diels-Alder reaction between cyclopentadiene and alkyl and cycloalkyl acrylates in the presence of new chiral catalysts, BBr 3?MentOEt, AlCl2OMent, BBr2OMent, and BBr(OMent)2, was studied. Optically active bicyclo[2.2.1]hept-2-ene- 5-carboxylates were synthesized. The influence of the reaction conditions on the total and optical yields and on the stereoselectivity of the adducts synthesized was examined. Nauka/Interperiodica 2006.
Mamedov
p. 1621 - 1625
(2008/02/07)

ZrOCl2·8H2O: An efficient, cheap and reusable catalyst for the esterification of acrylic acid and other carboxylic acids with equimolar amounts of alcohols
Esterifications of carboxylic acids with equimolar amount of alcohols could be efficiently catalyzed by ZrOCl2·8H2O. Acrylate esters were obtained in good yields under solvent-free conditions at ambient temperature. The esterification of other carboxylic acids with alcohols also proceeded at ambient temperature or at 50°C to afford esters in high yields. If the esterification was performed in toluene under azeotropic reflux conditions to remove water, both the catalytic activity of ZrOCl 2·8H2O and the rate of esterification could be increased greatly. Furthermore, in the present catalytic system, the esters could be easily separated from the reaction mixtures and the catalyst could be easily recovered and reused.
Sun, Hong-Bin,Hua, Ruimao,Yin, Yingwu
p. 263 - 271
(2007/10/03)

Process for preparing alkyl esters of (meth)acrylic acid
A process is described for continuously preparing alkyl esters of (meth)acrylic acid by reacting (meth)acrylic acid and alkanols having from 1 to 5 carbon atoms in homogeneous, liquid, solvent-free phase at elevated temperature and in the presence of an acidic esterification catalyst, in which the (meth)acrylic acid, the alkanol and the acidic esterification catalyst are fed to a reaction zone (5, 6), a reaction mixture (21) is discharged from the reaction zone (5, 6), and is introduced into a rectification unit I and separated by addition of water into a top stream (23), comprising the alkyl ester of (meth)acrylic acid, and a bottom stream (22), and a substream of the bottom stream (22) from the rectification unit I is fed to a residue dissociation unit IV, which comprises a dissociating boiler (61), and is separated therein into a top stream (29), which is recycled into the rectification unit I and a bottom stream (40), which is removed from the system, wherein the residue dissociation unit IV, as well as the dissociating boiler (61), further comprises a rectification column (62), the water content of the liquid obtained at the bottommost stage thereof being less than 0.1% by weight.
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Page/Page column 5

(2008/06/13)

PROCESS FOR PRODUCING (METH)ACRYLIC ACID DERIVATIVE
The present invention provides a method for efficiently using an aqueous solution of (meth) acrylic acid at a low concentration formed in a production/storage step of (meth)acrylic acid. In the present invention, a (meth)acrylic acid derivative is produced by using as a raw material an aqueous solution of (meth)acrylic acid formed by one or both of: a device which reduces a pressure of a gas comprising (meth) acrylic acid in production of (meth) acrylic acid; and a device which collects (meth)acrylic acid from a gas comprising (meth)acrylic acid.
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Page/Page column 7-8

(2008/06/13)

Method for storing (meth)acrylic acid or (meth)acrylic esters
There is provided a method for storing (meth)acrylic acid or (meth)acrylic esters in a storage tank for receiving or discharging the (meth)acrylic acid or (meth)acrylic esters, which is capable of storing the (meth)acrylic acid or (meth)acrylic esters for a long period of time. According to the method of the present invention, upon storing the (meth)acrylic acid or (meth)acrylic esters in the storage tank for receiving or discharging the (meth)acrylic acid or (meth)acrylic esters, a concentration of suspended particulate matters contained in a gas phase portion of the storage tank is controlled to not more than 0.01 mg/m3.
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Page/Page column 2-3

(2008/06/13)

Method for handling high-viscosity substances
There is provided a method for handling high-viscosity substances discharged from a production process of acrylic acid or esters thereof by gas-phase catalytic oxidation, which method is improved such that upon transporting the high-viscosity substances in a molten state to a storage tank through a pipeline, the retention or clogging of the high-viscosity substances in the pipeline can be effectively prevented without adding a solvent thereto, resulting in smooth transportation thereof through the pipeline. In the method for handling high-viscosity substances discharged from a production process of acrylic acid or esters thereof by gas-phase catalytic oxidation according to the present invention, when the high-viscosity substances are transported to a storage tank through a pipeline, contents of acrylic acid polymers and a polymerization inhibitor in the high-viscosity substances are controlled to not less than 40% by weight and not less than 4% by weight, respectively, and the high-viscosity substances are maintained at a temperature of not less than 110° C.
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Page/Page column 4

(2008/06/13)

CLEAVING OLIGOMERIC (METH)ACRYLIC ACID IN THE LIQUID PHASE AND UNDER PRESSURE
The invention relates to a method for cleaving a (meth)acrylic acid oligomer of structure (I), optionally in the presence of a cleaving agent of structure R3-OH or of structure (R4)2-N-H. The (meth)acrylic acid oligomer, together with the cleaving agent, is heated to a temperature of at least 50 °C and under a pressure of at least 1 bar. The invention also relates to the use of water, optionally with a protic compound serving as a cleaving agent, for cleaving (meth)acrylic acid oligomers, to a device for synthesizing (meth)acrylic acid, to the use of this device for producing (meth)acrylic acid, and to the (meth)acrylic acid produced while using said device.
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Page/Page column 24-25; 29; 36; sheet 1/3-3/3

(2010/02/13)

Nail varnish composition comprising at least one film-forming gradient copolymer and cosmetic process for making up and/or caring for the nails
A nail varnish composition comprising, in a cosmetically acceptable medium, at least one film-forming gradient copolymer comprising at least two different monomeric units and exhibiting a mass polydispersity index (PI) of less than or equal to 2.5, the composition being capable of forming a film having an adhesion corresponding to a detachment percentage of less than 45%; a cosmetic process for making up and/or caring for the nails comprising the application to the nails of the cosmetic composition.
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(2008/06/13)

METHODS OF MANUFACTURING DERIVATIVES OF β-HYDROXYCARBOXYLIC ACIDS
Preparation of derivatives of β-hydroxycarboxylic acid, including β-hydroxycarboxylic acid esters, α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acid, and alkoxy derivatives.
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Page/Page column 14

(2008/06/13)